WO2022168989A1 - Photochromic compound, photochromic composition, photochromic article, and eyeglasses - Google Patents

Abstract

Provided are a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. In general formula 1, R100 to R111, X1 and X2 each independently denote a hydrogen atom or a substituent group, and two or more substituent groups may bond to each other to form a ring structure. In general formula 2, R200 to R211, X3 and X4 each independently denote a hydrogen atom or a substituent group, and two or more substituent groups may bond to each other to form a ring structure. In general formula 3, R300 to R311, X5 and X6 each independently denote a hydrogen atom or a substituent group, and two or more substituent groups may bond to each other to form a ring structure.

Description

Photochromic compounds, photochromic compositions, photochromic articles and spectacles

The present invention relates to photochromic compounds, photochromic compositions, photochromic articles and spectacles.

A photochromic compound is a compound that has a property (photochromic performance) of coloring under irradiation with light in a wavelength range having photoresponsiveness and fading under non-irradiation. For example, Patent Literature 1 and Patent Literature 2 disclose naphthopyran-based compounds having photochromic properties.

WO2000/15631 WO1996/14596

For example, photochromic performance can be imparted to optical articles such as spectacle lenses by a method of incorporating a photochromic compound into a base material, a method of forming a layer containing a photochromic compound, or the like.

A photochromic compound, for example, undergoes structural transformation into a colored body through an excited state upon irradiation with light such as sunlight. The structure after structural conversion via light irradiation can be called a "color body". In contrast, the structure before light irradiation can be called a "colorless body". As for the colorless body, the term "colorless" is not limited to being completely colorless, but includes the case where the color is lighter than that of the colored body. A photochromic compound in which absorption of short-wavelength visible light around 380 nm is suppressed in a colorless state is preferable for providing an optical article with little coloration (for example, yellowishness) in a use environment such as a room.

An object of one aspect of the present invention is to provide a photochromic compound in which absorption of short-wavelength visible light is suppressed in a colorless state.

One aspect of the present invention relates to a photochromic compound represented by general formula 1 below.

In general formula 1, R ¹⁰⁰ to R ¹¹¹ , X ¹ and X ² each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.

Another aspect of the present invention relates to a photochromic compound represented by general formula 2 below.

In general formula 2, R ²⁰⁰ to R ²¹¹ , X ³ and X ⁴ each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.

Another aspect of the present invention relates to a photochromic compound represented by general formula 3 below.

In Formula 3, R ³⁰⁰ to R ³¹¹ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.

The structures of general formulas 1 to 3 are all colorless structures.

Further, one aspect of the present invention is one or more photochromic compounds selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. It relates to photochromic compositions containing compounds.

Further, one aspect of the present invention is one or more photochromic compounds selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. Photochromic articles containing compounds.

The photochromic compound represented by general formula 1, the photochromic compound represented by general formula 2, and the photochromic compound represented by general formula 3 are all pyran-based compounds having a triphenylene skeleton as a mother skeleton. As a result of intensive studies by the present inventors, it was newly found that these photochromic compounds absorb little short-wavelength visible light in a colorless state.

According to one aspect of the present invention, it is possible to provide a photochromic compound in which absorption of short-wavelength visible light is suppressed in a colorless state.

1 shows an NMR chart of synthesized exemplary compound 1. FIG. 1 shows absorption spectra of exemplary compound 1 and comparative compound 1 before and after ultraviolet irradiation.

In the present invention and this specification, the term "photochromic article" refers to an article containing a photochromic compound. The photochromic article according to one aspect of the present invention is one or more selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. of photochromic compounds. The photochromic compound can be included in the substrate of the photochromic article and/or can be included in the photochromic layer in a photochromic article having a substrate and a photochromic layer. A "photochromic layer" is a layer containing a photochromic compound.

In the present invention and the specification, the term "photochromic composition" refers to a composition containing a photochromic compound. The photochromic composition according to one aspect of the present invention is one selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. The above photochromic compound can be included and used for manufacturing a photochromic article according to one aspect of the present invention.

[Photochromic compound]
In general formulas 1 to 3, R ¹⁰⁰ to R ¹¹¹ , R ²⁰⁰ to R ²¹¹ , R ³⁰⁰ to R ³¹¹ and X ¹ to X ⁶ each independently represent a hydrogen atom or a substituent. In each general formula, two or more substituents may combine to form a ring structure.

In the present invention and the specification, various substituents, that is, any of R ¹⁰⁰ to R ¹¹¹ , R ²⁰⁰ to R ²¹¹ , R ³⁰⁰ to R ³¹¹ and X ¹ to X ⁶ in general formulas 1 to 3 The substituents to be obtained, and further, the substituents when each group described later has a substituent are each independently
Linear or branched alkyl groups having 1 to 18 carbon atoms such as hydroxy group, methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cyclic or bicyclic cyclic aliphatic alkyl groups, linear or branched alkoxy groups having 1 to 24 atoms such as methoxy, ethoxy, butoxy, non-aromatic groups having 1 to 24 atoms a cyclic substituent, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms such as a trifluoromethyl group, a linear or branched perfluoroalkoxy group such as a trifluoromethoxy group, a methylsulfide group, an ethylsulfide group, Linear or branched alkyl sulfide groups having 1 to 24 constituent atoms such as butyl sulfide group, phenyl group, naphthyl group, anthracenyl group, fluoranthenyl group, phenanthryl group, pyranyl group, perylenyl group, styryl group, fluorenyl group, etc. aryl group, aryloxy group such as phenyloxy group, arylsulfide group such as phenylsulfide group, pyridyl group, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, Dibenzothiophenyl group, carbazolyl group, diazolyl group, triazolyl group, quinolinyl group, phenothiazinyl group, phenoxazinyl group, phenazinyl group, thianthryl group, heteroaryl group such as acridinyl group, amino group (-NH ₂ ), monomethylamino group, etc. monoalkylamino group, dialkylamino group such as dimethylamino group, monoarylamino group such as monophenylamino group, diarylamino group such as diphenylamino group, piperidino group, morpholino group, thiomorpholino group, tetrahydroquinolino group, Cyclic amino groups such as tetrahydroisoquinolino groups, ethynyl groups, mercapto groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxy groups, cyano groups and fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. a substituent R ^m selected from the group consisting of halogen atoms; or
a substituent in which R ^m is further substituted with one or more identical or different R ^m ;
can be

An example of a substituent in which the above R ^m is further substituted with one or more identical or different R ^m is a terminal carbon atom of the alkoxy group further substituted with an alkoxy group, and a terminal carbon atom of the alkoxy group is further substituted with A structure in which an alkoxy group is substituted can be mentioned. Further, another example of the substituent in which the above R ^m is further substituted with one or more of the same or different R ^m is the same or different Structures in which R ^m is substituted can be mentioned. However, it is not limited to such an example.

In the present invention and this specification, the terms "carbon number" and "constituent atom number" refer to the numbers including the carbon number or the atomic number of the substituent with respect to a group having a substituent.

Further, in the present invention and this specification, any of R ¹⁰⁰ to R ¹¹¹ , R ²⁰⁰ to R ²¹¹ , R ³⁰⁰ to R ³¹¹ and X ¹ to X ⁶ in general formulas 1 to 3 Substituents that can be represented, furthermore, substituents when each group described later has a substituent can each independently be a solubilizing group. In the present invention and herein, "solubilizing group" refers to a substituent that can contribute to enhancing compatibility with any liquid or a specific liquid. Examples of solubilizing groups include alkyl groups containing linear, branched or cyclic structures having 4 to 50 carbon atoms, linear, branched or cyclic alkoxy groups having 4 to 50 atoms, and straight chains having 4 to 50 atoms. , a branched or cyclic silyl group, a silicon atom, a sulfur atom, a nitrogen atom, a phosphorus atom, or the like in part of the above groups, or a combination of two or more of the above groups. Substituents that can contribute to promoting thermal motion of the molecules of the compound are preferred. A compound having a solubilizing group as a substituent prevents the solute from solidifying by inhibiting the distance between the solute molecules from approaching each other. state can be created. Thus, a solubilizing group can liquefy a solute or increase the solubility of a compound bearing this substituent in a liquid. In one embodiment, the solubilizing group includes linear alkyl groups such as n-butyl, n-pentyl, n-hexyl, and n-octyl, branched alkyl groups such as tert-butyl, and cyclic alkyl groups. Certain cyclopentyl and cyclohexyl groups are preferred.

The above substituents are preferably methoxy, ethoxy, phenoxy, methylsulfide, ethylsulfide, phenylsulfide, trifluoromethyl, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, A substituent selected from the group consisting of a carbazolyl group, a phenothiazinyl group, a phenoxazinyl group, a phenazinyl group, an acridinyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholylno group, a thiomorpholino group, a cyano group, and a solubilizing group more preferably a methoxy group, a phenoxy group, a methylsulfide group, a phenylsulfide group, a trifluoromethyl group, a phenyl group, a dimethylamino group, a diphenylamino group, a piperidino group, a morpholylno group, a thiomorpholino group, a cyano group and possibly It can be a substituent selected from the group consisting of solubilizing groups.

Specific examples of substituents that can be represented by R ¹⁰⁰ to R ¹¹¹ in general formula 1, R ²⁰⁰ to R ²¹¹ in general formula 2, and R ³⁰⁰ to R ³¹¹ in general formula 3 include the exemplary compounds shown below. Included substituents may also be mentioned.

X ¹ and X ² in general formula 1, X ³ and X ⁴ in general formula 2, and X ⁵ and X ⁶ in general formula 3 each independently represent a hydrogen atom or a substituent, and represent a substituent; is preferred. Such substituents include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzofluorenyl group, and a substituted or unsubstituted fluoranthenyl group. , a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothiophenyl group. More preferably, ^B7 and ^B8 each independently represent an unsubstituted phenyl group or a substituted phenyl group. Substituted phenyl groups include, for example, methoxy group, methylsulfide group, amino group, dimethylamino group, piperidino group, morpholino group, thiomorpholino group, phenyl group, fluorine atom, chlorine atom, bromine atom, iodine atom and trifluoromethyl group. , a cyano group, and substituents included in the exemplary compounds listed below. Moreover, when the phenyl group has a plurality of substituents, two or more of these substituents may combine to form a ring. Specific examples of the ring to be formed include rings included in the exemplified compounds described later. In one embodiment, the substituted phenyl group preferably has one or two substituents, more preferably one. The substitution position of the substituent in the substituted phenyl group is relative to the carbon atom to which X1 and X2 in general formula ¹ are bonded, and to the carbon atom to which ^X3 and ^X4 in general formula ² are bonded. , can be a position that is ortho, meta or para with respect to the carbon atom to which X ⁵ and X ⁶ in general formula 3 are bonded, preferably para and/or meta. , more preferably in the para position.

The photochromic compound represented by general formula 1, the photochromic compound represented by general formula 2, and the photochromic compound represented by general formula 3 can all be used for producing photochromic articles. Specific examples of these compounds include the following compounds. However, the present invention is not limited to the following exemplary compounds.

The photochromic compound represented by general formula 1 can be synthesized by a known method. For the synthesis method, the following documents can be referred to, for example.特許第４８８４５７８号明細書、ＵＳ２００６／０２２６４０２Ａ１、ＵＳ２００６／０２２８５５７Ａ１、ＵＳ２００８／０１０３３０１Ａ１、ＵＳ２０１１／０１０８７８１Ａ１、ＵＳ２０１１／０１０８７８１Ａ１、米国特許第７５２７７５４号明細書、米国特許第７５５６７５１号明細書、ＷＯ２００１／６０８１１Ａ１、ＷＯ２０１３／０８６２４８Ａ１ , WO1996/014596A1, WO2001/019813A1, WO1995/16215A1, US Pat. No. 5,656,206 and WO2011/016582A1.

[Photochromic composition, photochromic article]
One aspect of the present invention is one or more photochromic compounds selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. Photochromic compositions comprising:
Further, one aspect of the present invention is one or more photochromic compounds selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. Photochromic articles containing compounds.

The photochromic composition and the photochromic article contain a photochromic compound selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. Only one species can be included, or two or more species (eg, two to four species) can be included. The photochromic article and the photochromic composition consist of a photochromic compound represented by the general formula 1, a photochromic compound represented by the general formula 2, and a photochromic compound represented by the general formula 3, with the total amount thereof being 100% by mass. A photochromic compound selected from the group (in the case where multiple types are included, the total thereof) can be included, for example, in an amount of about 0.1 to 15.0% by mass. However, it is not limited to the above range.

The photochromic article can have at least a base material. In one form, the photochromic compound can be included in the substrate of the photochromic article. The photochromic article can have a substrate and a photochromic layer, and the substrate and/or the photochromic layer can contain one or more photochromic compounds represented by the general formula (1). In the substrate and the photochromic layer, the photochromic compound can be contained only in the substrate in one embodiment, in the photochromic layer in another embodiment, or in the substrate and the photochromic layer in another embodiment. can be included in layers. Also, the substrate and the photochromic layer can contain only the photochromic compound as the photochromic compound, or can contain one or more other photochromic compounds. Other photochromic compounds include azobenzenes, spiropyrans, spirooxazines, naphthopyrans, indenonaphthopyrans, phenanthropyrans, hexaarylbisimidazoles, donor-acceptor Stenhaus adducts (DASA). , salicylideneanilines, dihydropyrenes, anthracene dimers, fulgides, diarylethenes, phenoxynaphthacenequinones, stilbenes and the like.

<Base material>
The photochromic article can contain a substrate selected according to the type of photochromic article. Examples of substrates include spectacle lens substrates such as plastic lens substrates and glass lens substrates. The glass lens substrate can be, for example, a lens substrate made of inorganic glass. Plastic lens substrates include styrene resins including (meth)acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, and polyether resins. , a urethane resin obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, and a (thio)epoxy compound having one or more disulfide bonds in the molecule. A cured product (generally called a transparent resin) obtained by curing the curable composition contained therein can be mentioned. As the lens substrate, an undyed one (colorless lens) may be used, or a dyed one (dyed lens) may be used. The refractive index of the lens substrate can be, for example, about 1.50 to 1.75. However, the refractive index of the lens substrate is not limited to the above range, and may be within the above range or vertically separated from the above range. Here, the refractive index refers to the refractive index for light with a wavelength of 500 nm. Further, the lens substrate may be a lens having refractive power (so-called prescription lens) or a lens without refractive power (so-called non-prescription lens).

For example, the photochromic composition can be a polymerizable composition. In the present invention and herein, a "polymerizable composition" is a composition containing one or more polymerizable compounds. At least one photochromic compound selected from the group consisting of the photochromic compound represented by the general formula 1, the photochromic compound represented by the general formula 2, and the photochromic compound represented by the general formula 3, and one polymerizable compound. A cured product of the polymerizable composition can be produced by molding the polymerizable composition containing at least the above by a known molding method. Such a cured product can be included as a substrate in the photochromic article and/or can be included as a photochromic layer. The curing treatment can be light irradiation and/or heat treatment. A polymerizable compound is a compound having a polymerizable group, and the polymerizable composition can be cured to form a cured product as the polymerization reaction of the polymerizable compound proceeds. The polymerizable composition can further include one or more additives (eg, polymerization initiators, etc.).

Spectacle lenses can be various lenses such as monofocal lenses, multifocal lenses, and progressive addition lenses. The type of lens is determined by the surface shape of both surfaces of the lens substrate. Also, the surface of the lens substrate may be convex, concave, or flat. In a normal lens substrate and a spectacle lens, the object-side surface is convex and the eyeball-side surface is concave. However, it is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens substrate, but may be provided on the eyeball-side surface.

<Photochromic layer>
The photochromic layer can be a layer provided directly on the surface of the substrate or indirectly via one or more other layers. The photochromic layer can be, for example, a cured layer obtained by curing a polymerizable composition. At least one photochromic compound selected from the group consisting of the photochromic compound represented by the general formula 1, the photochromic compound represented by the general formula 2, and the photochromic compound represented by the general formula 3, and one polymerizable compound. A photochromic layer can be formed as a cured layer obtained by curing a polymerizable composition containing at least the above. For example, by applying such a polymerizable composition directly on the surface of the substrate or applying it to the surface of a layer provided on the substrate and subjecting the applied polymerizable composition to a curing treatment, generally A photochromic layer as a cured layer containing one or more photochromic compounds selected from the group consisting of a photochromic compound represented by Formula 1, a photochromic compound represented by General Formula 2, and a photochromic compound represented by General Formula 3. can be formed. As the coating method, a known coating method such as a spin coating method, a dip coating method, a spray coating method, an inkjet method, a nozzle coating method, a slit coating method, or the like can be employed. The curing treatment can be light irradiation and/or heat treatment. The polymerizable composition can further comprise one or more additives (eg, polymerization initiators, etc.) in addition to one or more polymerizable compounds. As the polymerization reaction of the polymerizable compound proceeds, the polymerizable composition may be cured to form a cured layer.

The thickness of the photochromic layer can be, for example, 5 μm or more, 10 μm or more, or 20 μm or more, and can be, for example, 80 μm or less, 70 μm or less, or 50 μm or less.

<Polymerizable compound>
In the present invention and the specification, a polymerizable compound refers to a compound having one or more polymerizable groups in one molecule, and the term "polymerizable group" refers to a reactive group capable of undergoing a polymerization reaction. do. Examples of polymerizable groups include acryloyl groups, methacryloyl groups, vinyl groups, vinyl ether groups, epoxy groups, thiol groups, oxetane groups, hydroxy groups, carboxy groups, amino groups, isocyanate groups, and the like.

Examples of polymerizable compounds that can be used for forming the substrate and the photochromic layer include the following compounds.

(Episulfide compound)
An episulfide compound is a compound having two or more episulfide groups in one molecule. An episulfide group is a polymerizable group capable of ring-opening polymerization. Specific examples of episulfide compounds include bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide, bis(2,3-epithiopropyl) sulfide, bis(2,3-epithiopropyl) thio)methane, bis(2,3-epithiopropyl)disulfide, bis(2,3-epithiopropyldithio)methane, bis(2,3-epithiopropyldithio)ethane, bis(6,7-epithio- 3,4-dithiaheptyl) sulfide, bis(6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithiane-2,5-bis(2,3-epithiopropyldithiomethyl), 1,3 -bis(2,3-epithiopropyldithiomethyl)benzene, 1,6-bis(2,3-epithiopropyldithiomethyl)-2-(2,3-epithiopropyldithioethylthio)-4-thiahexane , 1,2,3-tris(2,3-epithiopropyldithio)propane, 1,1,1,1-tetrakis(2,3-epithiopropyldithiomethyl)methane, 1,3-bis(2, 3-epithiopropyldithio)-2-thiapropane, 1,4-bis(2,3-epithiopropyldithio)-2,3-dithiabutane, 1,1,1-tris(2,3-epithiopropyldithio ) methane, 1,1,1-tris(2,3-epithiopropyldithiomethylthio)methane, 1,1,2,2-tetrakis(2,3-epithiopropyldithio)ethane, 1,1,2, 2-tetrakis(2,3-epithiopropyldithiomethylthio)ethane, 1,1,3,3-tetrakis(2,3-epithiopropyldithio)propane, 1,1,3,3-tetrakis(2,3 -epithiopropyldithiomethylthio)propane, 2-[1,1-bis(2,3-epithiopropyldithio)methyl]-1,3-dithiethane, 2-[1,1-bis(2,3-epi Thiopropyldithiomethylthio)methyl]-1,3-dithiethane and the like can be mentioned.

(Thietanyl compound)
A thietanyl-based compound is a thietane compound having two or more thietanyl groups in one molecule. A thietanyl group is a polymerizable group capable of ring-opening polymerization. Some thietanyl-based compounds have an episulfide group along with multiple thietanyl groups. Such compounds are listed as examples of episulfide compounds above. Other thietanyl-based compounds include metal-containing thietane compounds having metal atoms in the molecule and non-metallic thietane compounds containing no metal.

Specific examples of nonmetallic thietane compounds include bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide, bis(3-thietanyl) trisulfide, bis(3-thietanyl) tetrasulfide, 1,4-bis (3-thietanyl)-1,3,4-trithibutane, 1,5-bis(3-thietanyl)-1,2,4,5-tetrathiapentane, 1,6-bis(3-thietanyl)-1, 3,4,6-tetrathiahexane, 1,6-bis(3-thietanyl)-1,3,5,6-tetrathiahexane, 1,7-bis(3-thietanyl)-1,2,4, 5,7-pentathiaheptane, 1,7-bis(3-thietanylthio)-1,2,4,6,7-pentathiaheptane, 1,1-bis(3-thietanylthio)methane, 1,2-bis (3-thietanylthio)ethane, 1,2,3-tris(3-thietanylthio)propane, 1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane, 1 , 11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-4,7-bis (3-thietanylthiomethyl)-3,6,9-trithiundecane, 1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9- Trithiundecane, 2,5-bis(3-thietanylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane, 2 ,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane, bisthietanylsulfide, bis(thietanylthio)methane, 3-[<(thietanylthio)methylthio>methylthio]thietane, bis Thietanyl disulfide, bis-thietanyl trisulfide, bis-thietanyl tetrasulfide, bis-thietanyl pentasulfide, 1,4-bis(3-thietanyldithio)-2,3-dithibutane, 1,1,1-tris(3-thietanyldithio) ) methane, 1,1,1-tris(3-thietanyldithiomethylthio)methane, 1,1,2,2-tetrakis(3-thietanyldithio)ethane, 1,1,2,2-tetrakis(3-thietanyl dithiomethylthio)ethane and the like.

As metal-containing thietane compounds, metal atoms such as Sn atoms, Si atoms, Ge atoms and Pb atoms, Group 14 atoms such as Sn atoms, Si atoms, Ge atoms and Pb atoms; Group 4 elements such as Zr atoms and Ti atoms; group atoms, group 12 atoms such as Zn atoms, and the like. Specific examples include alkylthio(thietanylthio)tin, bis(alkylthio)bis(thietanylthio)tin, alkylthio(alkylthio)bis(thietanylthio)tin, bis(thietanylthio)cyclic dithiotin compounds, and alkyl(thietanylthio)tin compounds.

Specific examples of alkylthio(thietanylthio)tin include methylthiotris(thietanylthio)tin, ethylthiotris(thietanylthio)tin, propylthiotris(thietanylthio)tin, and isopropylthiotris(thietanylthio)tin.

Specific examples of bis(alkylthio)bis(thietanylthio)tin include bis(methylthio)bis(thietanylthio)tin, bis(ethylthio)bis(thietanylthio)tin, bis(propylthio)bis(thietanylthio)tin, and bis(isopropylthio)tin. Examples include bis(thietanylthio)tin.

Specific examples of alkylthio(alkylthio)bis(thietanylthio)tin include ethylthio(methylthio)bis(thietanylthio)tin, methylthio(propylthio)bis(thietanylthio)tin, isopropylthio(methylthio)bis(thietanylthio)tin, and ethylthio(propylthio)tin. Examples include bis(thietanylthio)tin, ethylthio(isopropylthio)bis(thietanylthio)tin, isopropylthio(propylthio)bis(thietanylthio)tin and the like.

Specific examples of the bis(thietanylthio)cyclic dithiotin compounds include bis(thietanylthio)dithiastanetan, bis(thietanylthio)dithiastanenolan, bis(thietanylthio)dithiastanninan, bis(thietanylthio)trithiastanocane, and the like. can be exemplified.

Specific examples of alkyl(thietanylthio)tin compounds include methyltris(thietanylthio)tin, dimethylbis(thietanylthio)tin, butyltris(thietanylthio)tin, tetrakis(thietanylthio)tin, tetrakis(thietanylthio)germanium, and tris(thietanylthio)bismuth. I can give an example.

(Polyamine compound)
A polyamine compound is a compound having two or more _NH2 groups in one molecule, and can form a urea bond by reacting with a polyisocyanate, and can form a thiourea bond by reacting with a polyisothiocyanate. . Specific examples of polyamine compounds include ethylenediamine, hexamethylenediamine, isophoronediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, 1,3-propanediamine, putrescine, 2-(2-aminoethyl amino) ethanol, diethylenetriamine, p-phenylenediamine, m-phenylenediamine, melamine, 1,3,5-benzenetriamine and the like.

(Epoxy compound)
An epoxy-based compound is a compound having an epoxy group in its molecule. An epoxy group is a polymerizable group capable of ring-opening polymerization. Epoxy compounds are generally classified into aliphatic epoxy compounds, alicyclic epoxy compounds and aromatic epoxy compounds.

Specific examples of aliphatic epoxy compounds include ethylene oxide, 2-ethyloxirane, butyl glycidyl ether, phenyl glycidyl ether, 2,2′-methylenebisoxirane, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, Diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether Glycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol tetraglycidyl ether, tris(2-hydroxyethyl) isocyanurate and triglycidyl ether of.

Specific examples of alicyclic epoxy compounds include isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.

Specific examples of aromatic epoxy compounds include resol syndiglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, cresol novolac poly glycidyl ether and the like.

In addition to the above, an epoxy-based compound having a sulfur atom in the molecule can also be used along with the epoxy group. Such sulfur-containing epoxy compounds include linear aliphatic compounds and cycloaliphatic compounds.

Specific examples of chain aliphatic sulfur-containing atom epoxy compounds include bis(2,3-epoxypropyl) sulfide, bis(2,3-epoxypropyl) disulfide, and bis(2,3-epoxypropylthio)methane. , 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1 ,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)- 2-methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio) -2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3 -epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane, 2,2-bis(2,3-epoxypropylthiomethyl)-1- (2,3-epoxypropylthio)butane and the like.

Specific examples of cycloaliphatic sulfur-containing atom epoxy compounds include 1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1, 3-bis(2,3-epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-epoxypropylthiomethyl)-1, 4-dithiane, 2,5-bis[<2-(2,3-epoxypropylthio)ethyl>thiomethyl]-1,4-dithiane, 2,5-bis(2,3-epoxypropylthiomethyl)-2 ,5-dimethyl-1,4-dithiane and the like.

(Compound having a radically polymerizable group)
A compound having a radically polymerizable group is a radically polymerizable group. Examples of radically polymerizable groups include acryloyl groups, methacryloyl groups, allyl groups, and vinyl groups.

A compound having a polymerizable group selected from the group consisting of an acryloyl group and a methacryloyl group is hereinafter referred to as a "(meth)acrylate compound". Specific examples of (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene. Glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , ethylene glycol bisglycidyl (meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth) ) Acroxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane , 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, bisphenol F di(meth)acrylate, 1,1-bis(4-(meth)acryloxyethoxyphenyl)methane, 1, 1-bis(4-(meth)acroxydiethoxyphenyl)methane, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol di(meth) ) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol-tetra(meth)acrylate, methylthio(meth)acrylate, phenylthio(meth)acrylate, benzylthio(meth)acrylate, xylylene dithiol di(meth)acrylate, mercaptoethyl Examples include sulfide di(meth)acrylate, bifunctional urethane(meth)acrylate, and the like.

Specific examples of compounds having an allyl group (allyl compounds) include allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, methoxypolyethylene glycol allyl ether, and polyethylene glycol allyl ether. , methoxypolyethyleneglycol-polypropyleneglycol allyl ether, butoxypolyethyleneglycol-polypropyleneglycol allyl ether, methacryloyloxypolyethyleneglycol-polypropyleneglycol allyl ether, phenoxypolyethyleneglycol allyl ether, methacryloyloxypolyethyleneglycol allyl ether and the like.

Compounds having a vinyl group (vinyl compounds) include α-methylstyrene, α-methylstyrene dimer, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane). etc.

The photochromic article includes a protective layer for improving the durability of the photochromic article, an antireflection layer, a water-repellent or hydrophilic antifouling layer, an antifogging layer, and a primer layer for improving adhesion between layers. One or more of the layers known as functional layers can be included at any location.

The photochromic article can be an optical article. One form of optical article is a spectacle lens. Such spectacle lenses can also be called photochromic lenses or photochromic spectacle lenses. Examples of optical articles include goggle lenses, sun visor visor portions, helmet shield members, and the like. Optical articles having an antiglare function by coating the photochromic composition, which is a polymerizable composition, on a substrate for these optical articles, and subjecting the coated composition to a curing treatment to form a photochromic layer. can be obtained.

[glasses]
One aspect of the present invention relates to spectacles having a spectacle lens that is one form of the photochromic article. The details of the spectacle lenses included in these spectacles are as described above. By providing such spectacle lenses, the above spectacles can exhibit an anti-glare effect like sunglasses when the photochromic compound is colored by being irradiated with sunlight outdoors, and the photochromic compound can be colored when returned indoors. Transmittance can be recovered by fading. For the spectacles described above, a known technique can be applied to the configuration of the frame and the like.

The present invention will be further described below with reference to Examples. However, the present invention is not limited to the embodiments shown in Examples.

[Synthesis of Exemplified Compound 1]

Under an argon atmosphere, a dichloromethane solution (400 ml) of 4-chlorobenzoyl chloride (35.6 g, 200 mmol) was ice-cooled, and aluminum chloride (27.1 g, 200 mmol) was added. Subsequently, a dichloromethane solution (140 ml) of anisole (20.0 g, 190 mmol) was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 1N hydrochloric acid (200 ml) and ice, stirred, and separated. The organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated brine, and dried over sodium sulfate. Filtration and concentration gave Compound 1 (47.9 g) as a colorless solid.

Under an argon atmosphere, compound 1 (20.0 g, 81.0 mmol), _{Pd2dba3.CHCl3 (} 0.84 g, 0.81 mmol), _XPhos (1.16 g, 2.43 mmol), tert-butoxysodium (10. 9 g, 114 mmol) and morpholine (10.6 g, 122 mmol) in toluene (81 ml) were stirred at an external temperature of 105°C for 2 hours. After cooling, the mixture was filtered through celite, and unnecessary substances were washed with chloroform (200 ml). Concentration of the filtrate gave compound 2 (27.1 g) as a pale yellow solid.

Under an argon atmosphere, a tetrahydrofuran solution (420 ml) of Compound 2 (25.0 g, 84.0 mmol) was ice-cooled, and ethynylmagnesium bromide (250 ml, 0.5 M, 126 mmol) was added dropwise over 20 minutes. The mixture was stirred at an external temperature of 65°C for 2 hours. After cooling, the reaction mixture was quenched with saturated aqueous sodium chloride solution (300 ml) and extracted with ethyl acetate (200 ml×2). The organic layer was washed with saturated brine and dried over sodium sulfate. After filtration and concentration, the residue was purified by silica gel column chromatography (SiO ₂ : 400 g, heptane/ethyl acetate = 98/2 to 95/5) to obtain compound 3 (11.2 g) as a pale yellow solid.

Under an argon atmosphere, compound 4 (5.00 g, 17.9 mmol), compound 5 (4.54 g, 19.6 mol), potassium carbonate (7.40 g, 53.6 mmol), dichlorobis(triphenylphosphine)palladium(0. 63 g, 0.89 mmol) in DMSO (90 mL) was stirred at 140° C. for 23 hours. After cooling, water (200 mL) was added, extraction was performed with ethyl acetate/heptane (80 mL/40 mL x 2), and the organic layer was washed with water and saturated brine. After drying with sodium sulfate, it was filtered and concentrated. The obtained residue was purified by column chromatography (SiO ₂ : 100 g, heptane/ethyl acetate = 98/2 to 95/5) to obtain compound 6 (3.8 g).

Under an argon atmosphere, a THF solution (50 mL) of compound 6 (2.68 g, 11.6 mol) was cooled at an external temperature of −78° C., and TMEDA (2.63 mL, 17.4 mmol) and n-butyllithium (1.59 M , 11.0 mL, 17.4 mmol) was added. The external temperature was raised to 0° C. over 1 hour, and the mixture was stirred for 2 hours. Trimethyl borate (2.30 mL, 20.3 mmol) was added and stirred at room temperature for 4 hours. Under ice-cooling, acetic acid (1.33 mL, 23.2 mmol) and hydrogen peroxide solution (30%, 2.40 mL, 27.2 mmol) were added, and the mixture was stirred overnight at room temperature. An aqueous ammonium chloride solution was added, extracted with ethyl acetate (50 mL×2), the organic layer was washed with an aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. After filtration and concentration, the residue was purified by column chromatography (SiO ₂ : 400 g, heptane/ethyl acetate = 95/5 to 90/10) to obtain compound 7 (1.65 g).

Under an argon atmosphere, p-toluenesulfonic acid monohydrate (0.11 g, 0.58 mmol) was added, and the mixture was stirred at an external temperature of 120°C for 2 hours. After cooling, the mixture was filtered through celite, washed with ethyl acetate, and concentrated. The obtained residue was purified by column chromatography (SiO2: 400 g, heptane/ethyl acetate = 95/5 to 60/40). Exemplified Compound 1 was obtained by suspending and washing the obtained solid using diisopropyl ether (50 mL).

The obtained product was analyzed by the following method.

(1) Purity analysis Purity was calculated from the area ratio of high performance liquid chromatography (HPLC). LC-2040C manufactured by Shimadzu Corporation (YMC-Triart C18 100×2.1 mm, column temperature 40° C., PDA detector) was used as the HPLC apparatus. The mobile phase was acetonitrile/0.1% TFA H ₂ O=5/95-95/5 (7 min), 95/5 (3 min), and the flow rate was 0.4 ml/min.

(2) Structural identification LC-MS method was used for mass spectrometry. The LC-MS apparatus used was ACQUITY UPLC H-Class system (liquid chromatograph section), SQD2 (mass spectrometry section), and ACQUITY UPLC BEH C18 φ2.1×50 mm (column section) manufactured by Nippon Waters. As a result of mass spectrometry, the measured values shown in Table 1 were obtained for the calculated accurate masses shown in Table 1.
CHN elemental analysis was used for elemental analysis. A Perkin Elmer Series II 2400 was used as a CHN elemental analyzer. The calculated values shown in Table 1 were the actual values shown in Table 1.
JEOL ECS-400 was used for proton nuclear magnetic resonance ( ¹ H-NMR). Deuterated chloroform was used as the measurement solvent. FIG. 1 shows the obtained NMR chart.
From the above analysis results, it was confirmed that the target compound was produced comprehensively.

[Synthesis of Exemplary Compounds 2 to 5]
Exemplary compounds 2 to 5 were obtained by performing the same operation using the same synthetic method except that compound 7 and compound 3 (synthetic intermediate) were changed to the compounds shown in Table 1. Table 1 shows the molecular structure of each and the analysis results of the obtained compounds.

[Synthesis of Comparative Compound 1]
Comparative compound 1 was synthesized according to the method described in the above-mentioned literature for synthesis method. Table 1 shows the analysis results of Comparative Example Compound 1 obtained.

[Evaluation method]
<Evaluation of absorption characteristics before and after UV irradiation>
Each compound of Examples and Comparative Examples was dissolved in chloroform containing no stabilizer to prepare a chloroform solution of the compound.
A 1 cm square quartz spectroscopic cell containing the prepared solution was covered, and the absorbance was measured with a UV-visible spectrophotometer (Shimadzu UV-1900i, measurement wavelength: 800 to 250 nm, wavelength increments of 2 nm, high-speed mode). Absorbance measurements were performed at room temperature (20-25°C). Furthermore, this solution was once taken out from the spectrophotometer and irradiated with ultraviolet rays for 15 seconds using a UV-LED (a combination of LIGHTNINGCURE LC-L1V5 and L14310-120, output 70%) manufactured by Hamamatsu Photonics as an ultraviolet light source. The solution was stirred with a small stirrer during UV irradiation. Within 10 seconds after the end of ultraviolet irradiation, the sample was set again in the ultraviolet-visible spectrophotometer, spectroscopic measurement was performed under the same conditions, and the first absorption wavelength was confirmed.
The molar extinction coefficient ε (M ⁻¹ cm ⁻¹ ) at a wavelength of 380 nm before UV irradiation was read. This region corresponds to the absorption base of the uncolored body, and the molar extinction coefficient at 380 nm can be used as an indicator of the coloring of the uncolored body. If ε is less than 5000 M ⁻¹ cm ⁻¹ , it is preferable because the coloring becomes weak, and it is more preferable that it is less than 3000 M ⁻¹ cm ⁻¹ . Table 1 shows the read molar extinction coefficient values at 380 nm.
A new absorption peak appears in the visible light region (380 nm to 800 nm) because a colored body is formed after UV irradiation. Among the absorption peaks appearing in the visible region, the wavelength of the peak of absorption intensity observed at the longest wavelength is read and shown in Table 1 as "first absorption wavelength".
As an example, FIG. 2 shows absorption spectra before and after ultraviolet irradiation for Exemplified Compound 1 and Comparative Compound 1. FIG.

Exemplary Compounds 1 to 5 showed new absorption peaks in the visible light region after UV irradiation, confirming that these compounds exhibit photochromic properties. Compounds exhibiting photochromic properties in this way can be used for the production of various photochromic articles such as spectacle lenses.
Further, from the results shown in Table 1, it can be confirmed that Exemplified Compounds 1 to 5 absorb less short-wavelength visible light in the uncolored form than Comparative Example Compound 1, which does not have a triphenylene skeleton.

[Production and Evaluation of Spectacle Lenses]
<Preparation of photochromic composition (polymerizable composition)>
In a plastic container, 68 parts by mass of polyethylene glycol diacrylate, 12 parts by mass of trimethylolpropane trimethacrylate, and 20 parts by mass of neopentyl glycol dimethacrylate are mixed with a total of 100 parts by mass of (meth)acrylate. , (meth)acrylate mixtures were prepared. Illustrative compound 1 was mixed with 100 parts by mass of this (meth)acrylate mixture so as to be 7 parts by mass. Furthermore, a photopolymerization initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), an antioxidant [bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)] [ethylene bis(oxyethylene)] and a light stabilizer (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) are mixed and thoroughly stirred, and then a silane coupling agent (γ- methacryloxypropyltrimethoxysilane) was added dropwise with stirring. After that, it was defoamed by an automatic revolution type agitating and defoaming device.
A photochromic composition was prepared by the above method.

<Formation of primer layer>
A plastic lens substrate (manufactured by HOYA under the trade name EYAS: center thickness 2.5 mm, diameter 75 mm, spherical lens power -4.00) is immersed in an aqueous sodium hydroxide solution having a concentration of 10% by mass (liquid temperature 60°C) for 5 minutes. By doing so, it was washed with alkali, further washed with pure water, and dried. After that, a water-based polyurethane resin liquid (polycarbonate polyol-based polyurethane emulsion, viscosity of 100 cPs, solid content concentration of 38% by mass) was applied to the convex surface of the plastic lens substrate in an environment of room temperature and relative humidity of 40 to 60%. Using a spin coater MS-B150, a primer layer having a thickness of 5.5 μm was formed by spin coating at a rotation speed of 1500 rpm for 1 minute and air drying for 15 minutes.

<Deposition of photochromic layer>
The photochromic composition prepared above is dropped on the primer layer, and using Mikasa's MS-B150, the rotation speed is changed in slope mode from 500 rpm to 1500 rpm over 1 minute, and further 5 times at 1500 rpm. It was applied by a spin coating method using a program to rotate for 1 second. After that, the photochromic composition coated on the primer layer formed on the plastic lens substrate was irradiated with ultraviolet rays (main wavelength: 405 nm) for 40 seconds in a nitrogen atmosphere (oxygen concentration: 500 ppm or less), and this composition was was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 μm.
Thus, a photochromic article (spectacle lens) was produced.

<Evaluation of color density>
Luminous reflectance was obtained by the following method according to JIS T7333:2005.
The convex surface of the spectacle lens was irradiated with light from a xenon lamp as a light source through an aeromass filter for 15 minutes to color the photochromic layer. This irradiation light was applied so that the irradiance and the tolerance of the irradiance were the values shown in Table 2 as specified in JIS T7333:2005. The transmittance at the time of coloring was measured with a spectrophotometer manufactured by Otsuka Electronics.

<Evaluation of fading speed>
The fading speed was evaluated by the following method.
The transmittance (measurement wavelength: 550 nm) of the spectacle lens before light irradiation (uncolored state) was measured with a spectrophotometer manufactured by Otsuka Electronics. The transmittance measured here is called "initial transmittance".
Each spectacle lens was irradiated with light for 15 minutes through an aeromass filter using a xenon lamp as a light source to color the photochromic layer. This irradiation light was applied so that the irradiance and the tolerance of the irradiance were the values shown in Table ◯ as specified in JIS T7333:2005. The transmittance during this coloring was measured in the same manner as the initial transmittance. The transmittance measured here is called "coloring transmittance".
After that, the time required for the transmittance to reach [(initial transmittance−transmittance when colored)/2] from the time when light irradiation was stopped was measured.
The spectacle lens containing Exemplified Compound 1 had a luminous transmittance T% of 42% and a half life time of 4.5 minutes when colored.
From the above results, the spectacle lens is a spectacle lens (photochromic lens) exhibiting photochromic performance in which the luminous transmittance changes before and after irradiation with ultraviolet rays, and returns to the original state over time when the irradiation of ultraviolet rays is stopped. It was confirmed.

Finally, we summarize each of the aforementioned aspects.

According to one aspect, a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3 are provided.

In one embodiment, substituents that can be represented by any of R ¹⁰⁰ to R ¹¹¹ , R ²⁰⁰ to R ²¹¹ , R ³⁰⁰ to R ³¹¹ and X ¹ to X ⁶ in general formulas 1 to 3 are
a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a monocyclic or polycyclic cycloaliphatic alkyl group having 5 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 24 constituent atoms, A non-aromatic cyclic substituent having 1 to 24 atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms, a linear or branched perfluoroalkoxy group, a linear or branched group having 1 to 24 atoms branched alkylsulfide group, aryl group, aryloxy group, arylsulfide group, heteroaryl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, cyclic amino group, ethynyl group, mercapto a substituent R ^m selected from the group consisting of groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxy groups, cyano groups and halogen atoms; or
a substituent in which R ^m is further substituted with one or more identical or different R ^m ;
can be

According to one aspect, it contains at least one photochromic compound selected from the group consisting of a photochromic compound represented by general formula 1, a photochromic compound represented by general formula 2, and a photochromic compound represented by general formula 3. A photochromic composition is provided.

In one form, the photochromic composition can further contain a polymerizable compound.

According to one aspect, a photochromic article containing a cured product obtained by curing the photochromic composition is provided.

In one form, the photochromic article can have a substrate and a photochromic layer that is the cured product.

In one form, the photochromic article can be a spectacle lens.

In one form, the photochromic article can be a goggle lens.

In one form, the photochromic article can be a visor portion of a sun visor.

In one form, the photochromic article can be a helmet shield member.

According to one aspect, spectacles provided with the above spectacle lenses are provided.

Two or more of the various aspects and various forms described in this specification can be combined in any combination.

The embodiments disclosed this time should be considered illustrative in all respects and not restrictive. The scope of the present invention is indicated by the scope of the claims rather than the above description, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims.

One aspect of the present invention is useful in technical fields such as eyeglasses, goggles, sun visors, and helmets.

Claims (14)

A photochromic compound represented by the following general formula 1.

(In General Formula 1, R ¹⁰⁰ to R ¹¹¹ , X ¹ and X ² each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.) A photochromic compound represented by the following general formula 2.

(In general formula 2, R ²⁰⁰ to R ²¹¹ , X ³ and X ⁴ each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.) A photochromic compound represented by the following general formula 3.

(In general formula 3, R ³⁰⁰ to R ³¹¹ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a substituent, and two or more substituents may combine to form a ring structure.) The substituent is
a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a monocyclic or polycyclic cycloaliphatic alkyl group having 5 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 24 constituent atoms, A non-aromatic cyclic substituent having 1 to 24 atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms, a linear or branched perfluoroalkoxy group, a linear or branched group having 1 to 24 atoms branched alkylsulfide group, aryl group, aryloxy group, arylsulfide group, heteroaryl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, cyclic amino group, ethynyl group, mercapto a substituent R ^m selected from the group consisting of groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxy groups, cyano groups and halogen atoms; or
a substituent in which R ^m is further substituted with one or more identical or different R ^m ;
The photochromic compound according to any one of claims 1 to 3, which is A photochromic composition comprising one or more photochromic compounds selected from the group consisting of the photochromic compound of claim 1, the photochromic compound of claim 2, and the photochromic compound of claim 3. The substituent is
a hydroxy group, a linear or branched alkyl group having 1 to 18 carbon atoms, a monocyclic or polycyclic cycloaliphatic alkyl group having 5 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 24 constituent atoms, A non-aromatic cyclic substituent having 1 to 24 atoms, a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms, a linear or branched perfluoroalkoxy group, a linear or branched group having 1 to 24 atoms branched alkylsulfide group, aryl group, aryloxy group, arylsulfide group, heteroaryl group, amino group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group, cyclic amino group, ethynyl group, mercapto a substituent R ^m selected from the group consisting of groups, silyl groups, sulfonic acid groups, alkylsulfonyl groups, formyl groups, carboxy groups, cyano groups and halogen atoms; or
a substituent in which R ^m is further substituted with one or more identical or different R ^m ;
The photochromic composition according to claim 5, which is 7. The photochromic composition of claim 5 or 6, further comprising a polymerizable compound. A photochromic article comprising a cured product obtained by curing the photochromic composition according to claim 7 . 9. The photochromic article according to claim 8, comprising a substrate and a photochromic layer which is the cured product. 10. Photochromic article according to claim 8 or 9, which is a spectacle lens. 10. The photochromic article according to claim 8 or 9, which is a lens for goggles. 10. Photochromic article according to claim 8 or 9, which is a visor part of a sun visor. 10. The photochromic article according to claim 8 or 9, which is a helmet shield member. Spectacles comprising the spectacle lens according to claim 10.

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